Electroluminescent device, and display device comprising thereof

ABSTRACT

An electroluminescent device includes a first electrode and a second electrode facing each other; a hole transport layer between the first electrode and the second electrode; a light emitting layer including a first light emitting layer disposed between the hole transport layer and the second electrode and including a first quantum dot and a second light emitting layer between the first light emitting layer and the second electrode and including a second quantum dot; and an electron transport layer between the light emitting layer and the second electrode. Each of the first and second light emitting layers emits first light, each of the first and second quantum dots has a core-shell structure including one or more shells, and the first and second quantum dots have different numbers of shells from each other or have different total thicknesses of the one or more shells from each other.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Korean Patent Application No.10-2019-0123994 filed on Oct. 7, 2019, and all the benefits accruingtherefrom under 35 U.S.C. § 119, the content of which in its entirety isherein incorporated by reference.

BACKGROUND 1. Field

An electroluminescent device and a display device comprising thereof aredisclosed.

2. Description of the Related Art

A quantum dot is a nanocrystal of a semiconductor material with adiameter of several nanometers to several tens of nanometers, whichexhibits a quantum confinement effect. The quantum dot generatesstronger light in a narrow wavelength region than commonly usedphosphors. The quantum dot emits light while excited electron istransited from a conduction band to a valence band, and a wavelength ofthe emitted light is changed depending upon a particle size of thequantum dot even in the same material. As the quantum dot emits light ofa shorter wavelength with a smaller particle size, the quantum dot mayprovide light in a desirable wavelength region by adjusting its size.

In other words, a light emitting layer including the quantum dots andvarious types of electronic devices including the same may generallysave production costs, compared with an organic light emitting diodeusing a light emitting layer including a phosphorescent and/orfluorescent material, and desirable colors may be emitted by changingsizes of the quantum dots, without using other organic materials in thelight emitting layer for emitting other color lights.

Luminous efficiency of the light emitting layer including the quantumdots is determined by quantum efficiency of the quantum dots, a balanceof charge carriers, light extraction efficiency, and the like.

SUMMARY

Particularly, in order to improve the quantum efficiency, excitons maybe confined in the light emitting layer, but when the excitons are notconfined in the light emitting layer by a variety of factors, it maycause a problem such as exciton quenching.

An embodiment provides an electroluminescent device having improvedlife-span and/or luminous efficiency and a display device including thesame.

According to an embodiment, an electroluminescent device includes afirst electrode and a second electrode which face each other; a holetransport layer disposed between the first electrode and the secondelectrode; a light emitting layer including a first light emitting layerdisposed between the hole transport layer and the second electrode andincluding a first quantum dot, and a second light emitting layerdisposed between the first light emitting layer and the second electrodeand including a second quantum dot; and an electron transport layerdisposed between the light emitting layer and the second electrode,where each of the first light emitting layer and the second lightemitting layer emits first light, each of the first quantum dot and thesecond quantum dot has a core-shell structure, the core-shell structureincludes one or more shells, and the first quantum dot and the secondquantum dot have different numbers of shells from each other or havedifferent total thicknesses of the one or more shells from each other.

The core may include a first semiconductor nanocrystal and the shell mayinclude a second semiconductor nanocrystal having a compositiondifferent from a composition of the first semiconductor nanocrystal.

The first semiconductor nanocrystal and the second semiconductornanocrystal may independently include a Group II-VI compound that doesnot include Cd, a Group III-V compound, a Group IV-VI compound, a GroupIV element or compound, a Group compound, a Group I-II-IV-VI compoundthat does not include Cd, or a combination thereof.

The number of shells of the first quantum dot may be less than thenumber of shells of the second quantum dot.

The first quantum dot may have a core-single shell structure and thesecond quantum dot may include a core-multiple shell structure.

Hole transport capability per unit area of the first quantum dot may begreater than hole transport capability per unit area of the secondquantum dot, and electron transport capability per unit area of thefirst quantum dot is greater than electron transport capability per unitarea of the second quantum dot.

The total thickness of the one or more shells in the first quantum dotmay be greater than the total thickness of the one or more shells in thesecond quantum dot.

The total thickness of the one or more shells in the first quantum dotmay be about 1 nanometers (nm) to about 15 nm, and the total thicknessof the one or more shells in the second quantum dot may be about 1 nm toabout 10 nm.

Each of the first quantum dot and the second quantum dot may have acore-multishell structure, and a thickness of an outermost shell of themultishells of the first quantum dot may be greater than a thickness ofan outermost shell of the multishells of the second quantum dot.

The first quantum dot may have lower electron transport capability thanthe second quantum dot.

Hole transport capability per unit area of the first quantum dot may begreater than or equal to hole transport capability per unit area of thesecond quantum dot, and electron transport capability per unit area ofthe first quantum dot may be less than or equal to electron transportcapability per unit area of the second quantum dot.

The first light may belong to any one of a first wavelength region ofabout 380 nm to about 489 nm, a second wavelength region of about 490 nmto about 510 nm, a third wavelength region of about 511 nm to about 581nm, a fourth wavelength region of about 582 nm to about 610 nm, and afifth wavelength region of about 611 nm to about 680 nm.

A ligand including a compound derived from a metal halide, a compoundderived from a carboxylic acid, a compound derived from a thiol, or acombination thereof may be attached to a surface of each of the firstquantum dot and the second quantum dot.

Each of the first light emitting layer and the second light emittinglayer may have an average thickness of about 5 nm to about 30 nm.

An average thickness of the first light emitting layer may be greaterthan or equal to an average thickness of the second light emittinglayer.

The hole transport layer may include a poly(3,4-ethylenedioxythiophene)derivative, a poly(styrenesulfonate) derivative, a poly-N-vinylcarbazolederivative, a polyphenylenevinylene derivative, apolyparaphenylenevinylene derivative, a polymethacrylate derivative, apolyarylamine derivative, a polyaniline derivative, a polypyrrolederivative, a poly(9,9-dioctylfluorene) derivative, apoly(spiro-bifluorene) derivative, tris(4-carbazol-9-yl phenyl)amine(“TCTA”),N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(“TPD”), N,N′-di(naphthalen-1-yl)-N-N′-diphenyl-benzidine (“NPB”),tris(3-methylphenylphenylamino)-triphenylamine (“m-MTDATA”),dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile(“HAT-CN”), poly-TPD, NiO, MoO₃, or a combination thereof.

The electron transport layer may include inorganic materialnanoparticles, quinolone-based compounds, triazine-based compounds,quinoline-based compounds, triazole-based compounds, naphthalene-basedcompounds, or a combination thereof.

The electron transport layer may include a cluster layer composed ofinorganic material nanoparticles.

A hole injection layer may be further included between the firstelectrode and the hole transport layer.

According to another embodiment, a display device including theelectroluminescent device is provided.

An electroluminescent device having improved life-span and/or luminousefficiency and life-span and a display device including the same areprovided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of an electroluminescentdevice according to an embodiment,

FIGS. 2 and 3 are cross-sectional views showing the first quantum dot(FIG. 2) and the second quantum dot (FIG. 3) of the electroluminescentdevice according to the first embodiment, respectively,

FIGS. 4 and 5 are cross-sectional views showing the first quantum dot(FIG. 4) and the second quantum dot (FIG. 5) of the electroluminescentdevice according to the second embodiment, respectively,

FIG. 6 is a voltage-current density graph of HOD (Hole Only Device)according to Verification Examples 1 to 2,

FIG. 7 is a voltage-current density graph of HOD (Hole Only Device)according to Verification Examples 3 to 4,

FIG. 8 is a voltage-current density graph of HOD (Hole Only Device)according to Verification Examples 5 to 6,

FIG. 9 is a voltage-current density graph of HOD (Hole Only Device)according to Verification Examples 7 to 8,

FIG. 10 is a voltage-current density graph of the electroluminescentdevices according to Example 1 and Comparative Example 1,

FIG. 11 is a time-luminance graph of the electroluminescent devicesaccording to Example 1 and Comparative Example 1,

FIG. 12 is a time-voltage graph of the electroluminescent devicesaccording to Example 1 and Comparative Example 1,

FIG. 13 is a voltage-luminance graph of the electroluminescent devicesaccording to Example 2 and Comparative Example 2,

FIG. 14 is a luminance-external quantum efficiency (“EQE”) graph of theelectroluminescent devices according to Example 2 and ComparativeExample 2,

FIG. 15 is a time-luminance graph of the electroluminescent devicesaccording to Example 2 and Comparative Example 2, and

FIG. 16 is a time-voltage graph of the electroluminescent devicesaccording to Example 2 and Comparative Example 2.

DETAILED DESCRIPTION

Example embodiments of the present disclosure will hereinafter bedescribed in detail, and may be easily performed by a person having anordinary skill in the related art. However, this disclosure may beembodied in many different forms, and is not to be construed as limitedto the example embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc.,are exaggerated for clarity. Like reference numerals designate likeelements throughout the specification. It will be understood that whenan element such as a layer, film, region, or substrate is referred to asbeing “on” another element, it can be directly on the other element orintervening elements may also be present. In contrast, when an elementis referred to as being “directly on” another element, there are nointervening elements present.

It will be understood that, although the terms “first,” “second,”“third” etc. may be used herein to describe various elements,components, regions, layers and/or sections, these elements, components,regions, layers and/or sections should not be limited by these terms.These terms are only used to distinguish one element, component, region,layer or section from another element, component, region, layer orsection. Thus, “a first element,” “component,” “region,” “layer” or“section” discussed below could be termed a second element, component,region, layer or section without departing from the teachings herein.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. “At least one” is not to be construed as limiting “a” or“an.” “Or” means “and/or.” As used herein, the term “and/or” includesany and all combinations of one or more of the associated listed items.It will be further understood that the terms “comprises” and/or“comprising,” or “includes” and/or “including” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components, and/orgroups thereof.

As used herein, when a definition is not otherwise provided, “thickness”refers to “an average thickness”. The “average thickness” means anarithmetic mean value of thicknesses of measurement objects (e.g.,layers, etc.) obtained from scanning electron microscope images atrandom from several times to several tens of times.

As used herein, for an average diameter of a particle in the presentdisclosure, although it may be digitized by a measurement to show anaverage size of a group, the generally used method includes a modediameter showing the maximum value of the distribution, a mediandiameter corresponding to the center value of integral distributioncurve, a variety of average diameters (numeral average, length average,area average, mass average, volume average, etc.), and the like. As usedherein, unless particularly mentioning otherwise, an average particlediameter means to a numeral average diameter in the present disclosure,and it is obtained by measuring D50 (particle diameter at a position ofdistribution rate of 50 percentages (%)).

As used herein, “Group” refers to a group of Periodic Table.

As used herein, “Group II” refers to Group IIA and Group IIB, andexamples of Group II metal may be Cd, Zn, Hg, and Mg, but are notlimited thereto.

As used herein, examples of “Group II metal that does not include Cd”refers to a Group II metal except Cd, for example, Zn, Hg, Mg, etc.

As used herein, “Group III” refers to Group IIIA and Group IIIB, andexamples of Group III metal may be Al, In, Ga, and TI, but are notlimited thereto.

As used herein, “Group IV” refers to Group IVA and Group IVB, andexamples of a Group IV metal may be Si, Ge, and Sn, but are not limitedthereto. As used herein, the term “metal” may include a semi-metal suchas Si.

As used herein, “Group I” refers to Group IA and Group IB, and examplesmay include Li, Na, K, Rb, and Cs, but are not limited thereto.

As used herein, “Group V” refers to Group VA, and examples may includenitrogen, phosphorus, arsenic, antimony, and bismuth, but are notlimited thereto.

As used herein, “Group VI” refers to Group VIA, and examples may includesulfur, selenium, and tellurium, but are not limited thereto.

An electroluminescent device including quantum dots (hereinafterreferred to as a quantum dot electroluminescent device) are attractingattention as a next generation display device due to high colorreproducibility of quantum dots and ease of solution processing.

However, in the quantum dot electroluminescent device, the flow of holesin the light emitting layer including the quantum dots in general is notsmooth compared with the flow of electrons in the electric field of aconstant intensity. Accordingly, the quantum dot electroluminescentdevice may require improvement in the following matters.

For example, charges (electrons, holes) injected toward the lightemitting layer tend to be recombined mainly on the interface of the holetransport layer and the light emitting layer or inside of the holetransport layer and/or the light emitting layer near the interface.Herein, excitons inside the quantum dot electroluminescent device may betrapped and quenched by several energy levels generated on the interfaceof the hole transport layer and the light emitting layer and/or in aninternal conduction band of the hole transport layer and/or the lightemitting layer near the interface.

Alternatively, the injected electrons and holes may be recombined not inthe light emitting layer but in a non-light emitting layer (e.g., thehole transport layer) and thus form excitons. Herein, the excitonsformed in the non-light emitting layer do not contribute to lightemission of the device but are quenched and thus may deteriorateefficiency of the quantum dot electroluminescent device.

Alternatively, excess electrons not recombined among the injectedelectrons and holes are continuously present on the interface of thehole transport layer and the light emitting layer, and thus may causedeterioration of materials included in the light emitting layer and/orthe hole transport layer. In addition, the excess electrons may causesurface defects of the interface of the hole transport layer and/or thelight emitting layer. These surface defects may quench the excitons andin addition, accelerate deterioration of the device, when driven at aconstant current.

Accordingly, the present inventors researched on a method of securing astable hole-electron balance inside the quantum dot electroluminescentdevice and confining excitons in the light emitting layer, and thusimproving luminous efficiency and life-span characteristics of thedevice.

As a result, the present inventors discovered that a stablehole-electron balance in the device may be secured, and also arecombination position of electrons and holes may be adjusted into thelight emitting layer to realize excellent luminous efficiency andlife-span characteristics, by configuring the light emitting layer ofthe quantum dot electroluminescent device as a dual layer andconfiguring the quantum dots of each layer to have a differentcore-shell structure, for example, such that the number of shells and/orthe total thickness of the shells are different from each other.

Thus, referring to FIG. 1, a schematic configuration of anelectroluminescent device according to an embodiment is described.

FIG. 1 is a cross-sectional view schematically showing anelectroluminescent device according to an embodiment.

An electroluminescent device 10 according to an embodiment includes afirst electrode 110 and a second electrode 160 facing each other, a holetransport layer 130 disposed between the first electrode 110 and thesecond electrode 160, a hole injection layer 120 that is disposedbetween the first electrode 110 and the hole transport layer 130 and isoptionally omitted in consideration of the relationship with eachconstituent element, a light emitting layer 140 disposed between thehole transport layer 130 and the second electrode 160, and an electrontransport layer 150 disposed between the light emitting layer 140 andthe second electrode 160.

In an embodiment, the light emitting layer 140 may include a first lightemitting layer 141 disposed between the hole transport layer 130 and thesecond electrode 160 and including first quantum dots 141 a, and asecond light emitting layer 142 disposed between the first lightemitting layer 141 and the second electrode 160 and including secondquantum dots 142 a.

That is, the electroluminescent device 10 has a stacked structure inwhich the hole injection layer 120, the hole transport layer 130, thelight emitting layer 140 including the first light emitting layer 141and the second light emitting layer 142, and the electron transportlayer 150 are sequentially disposed between the first electrode 110 andthe second electrode 160.

In an embodiment, the first electrode 110 may be directly connected to adriving power source such that the first electrode 110 may function toflow current to the light emitting layer 140. The first electrode 110may include a material having high light transmittance in at leastvisible light wavelength region, but the invention is not limitedthereto. In another embodiment, the first electrode 110 may include amaterial having high light transmittance in an infrared or ultraviolet(“UV”) wavelength region. For example, the first electrode 110 may be anoptically transparent material.

In an embodiment, the first electrode 110 may include molybdenum oxide,tungsten oxide, vanadium oxide, rhenium oxide, niobium oxide, tantalumoxide, titanium oxide, zinc oxide, nickel oxide, copper oxide, cobaltoxide, manganese oxide, chromium oxide, indium oxide, or a combinationthereof.

However, the first electrode 110 according to an embodiment is notnecessarily limited thereto but may include a material further havinghigh light transmittance with respect to light in an infrared orultraviolet (UV) wavelength region or a semi-permeable materialselectively transmitting light in a particular wavelength region or mayconduct a function of reflecting light in a visible light wavelengthregion and turning it back toward the second electrode 160.

In an embodiment, the first electrode 110 may be disposed on thesubstrate 100 as shown in FIG. 1. The substrate 100 may be a transparentinsulating substrate or may be made of or include a ductile material.The substrate 100 may include glass or polymer material of a film havinga glass transition temperature of greater than about 150 degrees Celsius(° C.). For example, it includes a COC (cyclo olefin copolymer) or COP(cyclo olefin polymer) based material.

In an embodiment, the substrate 100 may support the hole injection layer120, the transport layer 130, the light emitting layer 140, and theelectron transport layer 150 disposed between the first electrode 110and the second electrode 160. However, the substrate 100 of theelectroluminescent device 10 according to an embodiment may not bedisposed under the first electrode 110, but the substrate 100 may bedisposed on the second electrode 160 or may be omitted.

The second electrode 160 includes an optically transparent material andmay function as a light-transmitting electrode to transmit lightgenerated in the light emitting layer 140. In an embodiment, the secondelectrode 160 may include at least one selected from silver (Ag),aluminum (Al), copper (Cu), gold (Au), and an alloy thereof, molybdenumoxide, tungsten oxide, vanadium oxide, rhenium oxide, niobium oxide,tantalum oxide, titanium oxide, zinc oxide, nickel oxide, copper oxide,cobalt oxide, manganese oxide, chromium oxide, indium oxide, or acombination thereof.

However, the second electrode 160 according to an embodiment is notlimited thereto but may include a semi-permeable material selectivelytransmitting light in a particular wavelength region, or conduct afunction of reflecting light in a visible light wavelength region andturning it back toward the first electrode 110 in another embodiment.

When the second electrode 160 functions as a reflecting electrode, thefirst electrode 110 may be a light-transmitting electrode formed of orinclude a material transmitting light in at least visible lightwavelength region or a semi-permeable electrode selectively transmittinglight in a particular wavelength region.

Each of the first electrode 110 and the second electrode 160 may beformed by depositing a material for forming an electrode on thesubstrate 100 or an organic layer by a method such as sputtering.

As shown in FIG. 1, an electroluminescent device 10 according to anembodiment may have a structure where the substrate 100 and each ofconstituent elements are disposed in the above stack order.

However, the electroluminescent device 10 according to an embodiment isnot necessarily limited thereto but may have various structures within arange of satisfying the aforementioned order of disposing eachconstituent element. For example, when the substrate 100 is disposed notbeneath the first electrode 110 but on the second electrode 160, theelectroluminescent device 10 may have an inverted structure.

The hole injection layer 120 may be disposed between the first electrode110 and the second electrode 160, for example, between the firstelectrode 110 and the hole transport layer 130 that will be describedlater, for example, directly on the first electrode 110. The holeinjection layer 120 may supply holes into the light emitting layer 140together with the hole transport layer 130. However, the hole injectionlayer 120 may be omitted considering the thickness and the material ofthe hole transport layer 130.

The hole injection layer 120 may be formed of or include a p-typesemiconductor or a material doped with a p-type semiconductor. Examplesof the hole injection layer 120 may includepoly(3,4-ethylenedioxythiophene) (“PEDOT”) or a derivative thereof,poly(styrene sulfonate) (“PSS”) or a derivative thereof,poly-N-vinylcarbazole (“PVK”) or a derivative thereof,polyphenylenevinylene or a derivative thereof, polyparaphenylenevinylene(“PPV”) or a derivative thereof, polymethacrylate or a derivativethereof, poly(9,9-dioctylfluorene) or a derivative thereof,poly(spiro-bifluorene) or a derivative thereof, tris(4-carbazol-9-ylphenyl)amine (TCTA),N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(TPD), N,N′-di(naphthalen-1-yl)-N-N′-diphenyl-benzidine (NPB),tris(3-methylphenylphenylamino)-triphenylamine (m-MTDATA),dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile(HAT-CN), poly-TPD, a metal oxide such as NiO or MoO₃, or a combinationthereof, but the invention is not necessarily limited thereto.

The hole transport layer 130 may be disposed between the first electrode110 and the second electrode 160, for example, on the first electrode110, for example, on the first electrode 110 and the hole injectionlayer 120. The hole transport layer 130 may provide and transport holesinto the light emitting layer 140. The hole transport layer 130 may beformed directly under the light emitting layer 140, and specificallyunder the first light emitting layer 141 to directly contact the lightemitting layer 140.

In an embodiment, the hole transport layer 130 may include a materialhaving a hole transporting property. The material having the holetransporting property may be a p-type semiconductor, or a material dopedwith a p-type semiconductor. The material having the hole transportingproperty is not limited to a specific material but may be a polymer, anoligomer, a metal oxide, or a combination thereof.

Examples of the material having the hole transporting property mayinclude a poly(3,4-ethylenedioxythiophene) derivative, a poly(styrenesulfonate) derivative, a poly-N-vinylcarbazole derivative, apolyphenylenevinylene derivative, a polyparaphenylenevinylenederivative, a polymethacrylate derivative, a polyarylamine derivative, apolyaniline derivative, a polypyrrole derivative, apoly(9,9-dioctylfluorene) derivative, a poly(spiro-bifluorene)derivative, tris(4-carbazol-9-yl phenyl)amine (TCTA),N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(TPD), N,N′-di(naphthalen-1-yl)-N-N′-diphenyl-benzidine (NPB),tris(3-methylphenylphenylamino)-triphenylamine (m-MTDATA),dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile(HAT-CN), poly-TPD, NiO, MoO₃, or a combination thereof, but theinvention is not necessarily limited thereto.

In an embodiment, a thickness of the hole transport layer 130 may bevaried in consideration of hole-electron balance with the hole injectionlayer 120, the hole transport layer 130, and/or the light emitting layer140 in the device 10. The thickness of the hole transport layer 130 maybe, for example, greater than or equal to about 10 nanometers (nm), forexample, greater than or equal to about 15 nm, or greater than or equalto about 20 nm and for example, less than or equal to about 80 nm, lessthan or equal to about 70 nm, less than or equal to about 60 nm, or lessthan or equal to about 50 nm, for example, about 10 nm to about 80 nm,about 10 nm to about 70 nm, about 10 nm to about 60 nm, about 10 mm toabout 50 nm, about 10 nm to about 40 nm, or about 20 nm to about 40 nm.

For example, the hole transport layer 130 may be formed in a wet coatingmethod such as spin coating and the like. For example, both of the holetransport layer 130 and the light emitting layer 140, and specificallyhole transport layer 130 and the first light emitting layer 141 may beformed in a wet coating method. In this way, the hole transport layer130 and/or the first light emitting layer 141 may be formed in a simpleprocess.

In addition, in an embodiment, the hole transport layer 130 and thefirst light emitting layer 141 may be made of or include materialshaving relatively different solubilities. For example, the holetransport layer 130 may be prepared using a material having excellentsolubility for an aromatic non-polar solvent, while the first lightemitting layer 141 may be prepared using a material having excellentsolubility for an aliphatic non-polar solvent. Accordingly, even thoughthe hole transport layer 130 and the first light emitting layer 141 aredirectly contacted using a solution process, the first light emittinglayer 141 may be formed without surface damage of the hole transportlayer 130, due to the different solubilities of the hole transport layer130 and the first light emitting layer 141.

In an embodiment, for example, when apoly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4′-(N-4-butylphenyl)diphenylamine)](“TFB”) polymer film is formed as the hole transport layer 130, aprecursor solution including a TFB precursor polymer and an aromaticnon-polar solvent (e.g., toluene, xylene, etc.) is spin-coated on thefirst electrode 110 or the hole injection layer 120, thermal treatmentis performed in an inert gas atmosphere of N₂ or in a vacuum at atemperature of about 150° C. to about 1800° C. for about 30 minutes toform a hole transport layer 130 made of TFB, and the first lightemitting layer 141 may be easily formed thereon using an aliphaticnon-polar solvent (for example, octane, nonane, cyclohexane, etc.) usinga solution process.

As such, when the hole transport layer 130 and the first light emittinglayer 141 are configured to have different relative solubilities, theformation of the hole transport layer 130 and the first light emittinglayer 141 using a solution process is more easily performed, and thesurface damage of the hole transport layer 130 by organic solvents maybe minimized during the subsequent formation of the first light emittinglayer 141.

The light emitting layer 140 may be disposed between the hole transportlayer 130 and the second electrode 160, for example, disposed on thehole transport layer 130, for example, directly disposed on the holetransport layer 130, and may include quantum dots.

In an embodiment, the light emitting layer 140 may include the firstlight emitting layer 141 and the second light emitting layer 142 asdescribed above. In an embodiment, each of the first light emittinglayer 141 and the second light emitting layer 142 may include quantumdots. Hereinafter, the quantum dots included in the first light emittinglayer 141 is referred to as first quantum dots 141 a, and the quantumdots included in the second light emitting layer 142 is referred to assecond quantum dots 142 a.

The light emitting layer 140 is a site where electrons and holestransported by a current supplied from the first electrode 110 and thesecond electrode 160 are combined, the electrons and holes are combinedin the light emitting layer 140 to generate excitons, and the generatedexcitons are transited from an exited state to a ground state to emitlight in a wavelength corresponding to the size of the quantum dot. Thatis, the quantum dots may endow the light emitting layer 140 with anelectro-luminescence function.

Particularly, since the quantum dots have a discontinuous energy bandgapby the quantum confinement effect, incident light may be converted intolight having a particular wavelength and then radiated. Accordingly, thelight emitting layer 140 including the quantum dots may produce lighthaving excellent color reproducibility and color purity.

In an embodiment, the light emitting layer 140 may emit light belongingto a predetermined wavelength region by the quantum dot. In anembodiment, each of the first light emitting layer 141 and the secondlight emitting layer 142 may emit first light. That is, the first andsecond light emitting layers 141 and 142 may emit light (i.e., firstlight) belonging to the same wavelength region. In an embodiment, thefirst light may be a wavelength region belonging to an ultraviolet lightregion and/or a visible light region, for example, a wavelength regionbelonging to the visible light region. The first light may belong to,for example, one of a first wavelength region of about 380 nm to about489 nm, a second wavelength region of about 490 nm to about 510 nm, athird wavelength region of about 511 nm to about 581 nm, a fourthwavelength region of about 582 nm to about 610 nm, and a fifthwavelength region of about 620 nm to about 680 nm.

In an embodiment, each of the first quantum dots 141 a and the secondquantum dots 142 a may emit blue light belonging to a first wavelengthregion of about 380 nm to about 489 nm. In this case, the light emittinglayer 140 may be a blue light emitting layer.

Alternatively, each of the first quantum dots 141 a and the secondquantum dots 142 a may emit red light belonging to a fifth wavelengthregion of about 620 nm to about 680 nm. In this case, the light emittinglayer 140 may be a red light emitting layer.

In an embodiment, materials of the first and second quantum dots 141 aand 142 a are not particularly limited, and known or commerciallyavailable quantum dots may be used.

In an embodiment, each of the first quantum dots 141 a and the secondquantum dots 142 a may have a core-shell structure.

In an embodiment, for each of the first quantum dots 141 a and thesecond quantum dots 142 a, the core may include a first semiconductornanocrystal, and the shell may include a second semiconductornanocrystal having a composition different from the composition of thefirst semiconductor nanocrystal.

In an embodiment, in the interface between the core and the shell, theshell may have a concentration gradient where a concentration ofelement(s) in the shell decreases toward the center. In an embodiment,the quantum dots may have a structure (core-single shell structure)including one core and one layer of shell surrounding it. In this case,the single shell structure may have a single composition orconcentration gradient.

Alternatively, at least one of the first quantum dots 141 a and thesecond quantum dots 142 a may have a structure (core-multishellstructure) including one core and a multi-layered shell surrounding thecore. Herein, the multi-layered shell structure has a structure of twoor more shells, and each layer may have a single composition or an alloyor may have a concentration gradient.

As such, when each of the first quantum dots 141 a and the secondquantum dots 142 a has a core-shell structure (e.g., a core-single shellstructure and/or a core-multi-layered shell structure), a materialcomposition constituting the shell may have a larger bandgap energy thana material composition constituting the core, In the case ofconstructing a multi-layered shell, an outer shell far from the core mayhave a larger bandgap energy than an inner shell close to the core. As aresult, a more effective quantum confinement may be obtained by usingquantum dots having a core-shell structure.

In an embodiment, the first semiconductor nanocrystal included in thecore and the second semiconductor nanocrystal included in the shell mayindependently include a Group II-VI compound that does not include Cd, aGroup III-V compound, a Group IV-VI compound, a Group IV element orcompound, a Group compound, a Group I-II-IV-VI compound that does notinclude Cd, or a combination thereof. That is, each of the first andsecond quantum dots 141 a and 142 a may be a cadmium-free quantum dot.Like this, when the first and second quantum dots 141 a and 142 aconsist of cadmium-free materials, they have no toxicity compared with aconventional cadmium-based quantum dots and thus are not dangerous andare environmentally-friendly.

The Group II-VI compound may be selected from a binary element compoundselected from ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, and amixture thereof; a ternary element compound selected from ZnSeS, ZnTeSe,ZnTeS, HgSeS, HgTeSe, HgTeS, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, and amixture thereof; and a quaternary element compound selected fromHgZnTeS, HgZnSeS, HgZnTeSe, and a mixture thereof. The Group II-VIcompound may further include a Group III metal.

The Group III-V compound may be selected from a binary element compoundselected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP,InAs, InSb, and a mixture thereof; a ternary element compound selectedfrom GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb,InNP, InNAs, InNSb, InPAs, InPSb, InZnP, and a mixture thereof; and aquaternary element compound selected from GaAlNP, GaAlNAs, GaAlNSb,GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP,InAlNAs, InAlNSb, InAlPAs, InAlPSb, and a mixture thereof. The GroupIII-V compound may further include a Group II metal (e.g., InZnP).

The Group IV-VI compound may be selected from a binary element compoundselected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, and a mixture thereof; aternary element compound selected from SnSeS, SnSeTe, SnSTe, PbSeS,PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and a mixture thereof; and aquaternary element compound selected from SnPbSSe, SnPbSeTe, SnPbSTe,and a mixture thereof. Examples of the Group compound may be CuInSe₂,CuInS₂, CuInGaSe, and CuInGaS. However, the examples according to theinvention are not limited thereto. Examples of the Group I-II-IV-VIcompound may be CuZnSnSe and CuZnSnS. However, the examples according tothe invention are not limited thereto. Examples of the Group IV compoundmay be a single substance selected from Si, Ge, and a mixture thereof;and a binary element compound selected from SiC, SiGe, and a mixturethereof.

The binary element compound, the ternary element compound, or thequaternary element compound each exists in a uniform concentration inthe particle (i.e., quantum dot) or in partially differentconcentrations in the same particle.

The first and second quantum dots 141 a and 142 a may have independentlyquantum efficiency of greater than or equal to about 10%, for example,greater than or equal to about 20%, greater than or equal to about 30%,greater than or equal to about 40%, greater than or equal to about 50%,greater than or equal to about 60%, greater than or equal to about 70%,greater than or equal to about 90%, or even 100%.

In a display, the first and second quantum dots 141 a and 142 a may havea relatively narrow emission wavelength spectrum so as to improve colorpurity or color reproducibility. The first and second quantum dots 141 aand 142 a may have independently a full width at half maximum (“FWHM”)of an emission wavelength spectrum of, for example, less than or equalto about 45 nm, less than or equal to about 40 nm, less than or equal toabout 35 nm, or less than or equal to or about 30 nm. Within the ranges,color purity or color reproducibility of a device may be improved.

The first and second quantum dots 141 a and 142 a may independently havean average particle diameter (the longest size of the particle if anon-spherically shaped particle) of about 1 nm to about 100 nm. Forexample, the first and second quantum dots 141 a and 142 a mayindependently have an average particle diameter (the longest size of theparticle if a non-spherically shaped particle) of, for example, about 1nm to about 20 nm, about 1 nm to about 15 nm, about 1 nm to about 14 nm,about 1 nm to about 13 nm, about 1 nm to about 12 nm, about 1 nm toabout 11 nm, or about 1 nm to about 10 nm.

In addition, the shapes of the first and second quantum dots 141 a and142 a may be general shapes in this art and thus may not be particularlylimited. For example, the quantum dots may have a spherical, oval,tetrahedral, pyramidal, cuboctahedral, cylinderical, polyhedral,multi-armed, or cube nanoparticle, nanotube, nanowire, nanofiber,nanosheet, or a combination thereof. The quantum dots may have anycross-sectional shape.

The commercially available quantum dots may be used as the first andsecond quantum dots 141 a and 142 a, or the first and second quantumdots 141 a and 142 a may be synthesized in any method. For example,several nanometer-sized quantum dots may be synthesized according to awet chemical process. In the wet chemical process, precursors react inan organic solvent to grow crystal particles, and the organic solvent orsurfactants for forming ligands may coordinate the surfaces of thequantum dots, controlling the growth of the crystal. Examples of theorganic solvent and the surfactants for forming ligands are known.

The organic solvent and the surfactants for forming ligands may beselected appropriately. Examples of the organic solvent may include C6to C22 primary amine such as hexanedecylamine; C6 to C22 secondary aminesuch as dioctylamine; C6 to C40 tertiary amine such as trioctylamine;nitrogen-containing heterocyclic compounds such as pyridine; C6 to C40olefin such as octadecene; C6 to C40 aliphatic hydrocarbon such ashexane, octane, hexanedecane, octadecane, or squalane; aromatichydrocarbon substituted with a C6 to C30 alkyl group such asphenyldodecane, phenyltetradecane, or phenyl hexanedecane; primary,secondary, or tertiary phosphine (e.g., trioctylphosphine) substitutedwith at least one (e.g., 1, 2, or 3) C6 to C22 alkyl group; phosphineoxide (e.g. trioctylphosphineoxide) substituted with at least one (e.g.,1, 2, or 3) C6 to C22 alkyl group; C12 to C22 aromatic ether such asphenyl ether, benzyl ether; or a combination thereof.

Examples of the surfactants for forming ligands may include RCOOH, RNH₂,R₂NH, R₃N, RSH, RH₂PO, R₂HPO, R₃PO, RH₂P, R₂HP, R₃P, ROH, RCOOR′,RPO(OH)₂, RHPOOH, RHPOOH (where, R and R′ are independently hydrogen, aC1 to C40 substituted or unsubstituted aliphatic hydrocarbon, or C6 toC40 substituted or unsubstituted aromatic hydrocarbon, or a combinationthereof, and in each ligand, at least one R is not hydrogen), or acombination thereof, but the invention is not limited thereto.

Since organic solvents coordinated to the surfaces of the quantum dotsmay affect stability in the device, excess materials (e.g., organicsolvents, surfactants for forming ligands, or combinations thereof) thatare not coordinated to the surfaces of the nanocrystals may be removedby excessively pouring them into a non-solvent and centrifuging theresultant mixture. Specific examples of the non-solvent include, but arenot limited to, acetone, ethanol, and methanol. After removing excessmaterial, the amount of materials coordinated to the surfaces of thequantum dots may be less than or equal to about 50 percentages by weight(wt %), for example, less than or equal to about 30 wt %, less than orequal to about 20 wt %, or less than or equal to about 10 wt % of theweight of the quantum dots. The materials coordinated to the surfaces ofthe quantum dots may include ligands, organic solvents, or a combinationthereof. The materials coordinated to the surfaces of the quantum dots,specifically the ligands, may impart dispersibility to the quantum dots.

In an embodiment, at least a portion of the surfaces of the first andsecond quantum dots 141 a and 142 a may have ligands attached thereto.In an embodiment, examples of the ligand may be a compound derived froma metal halide, a compound derived from a carboxylic acid, a compoundderived from thiol, or a combination thereof.

The ligand may be chemically bound to the surface of the quantum dots,electrostatic attraction, that is, a dispersing force (e.g., van derWaals bond) may be applied to the surface of the quantum dots, or bothbinding forms may exist. In an embodiment, the dispersing force may beacting between the ligand and the surface of the quantum dots. Forexample, when the ligand is a hydrophobic ligand, the hydrophobic ligandmay include a moiety to which a dispersing force with the surface of theattached quantum dots is applied and a hydrophobic functional group thatimparts hydrophobicity. In an embodiment, examples of the hydrophobicligand may be a compound derived from a carboxylic acid, a compoundderived from thiol, or a combination thereof.

Examples of the hydrophobic moiety may include a C4 to C20 alkyl group,a C4 to C20 alkenyl group, a C4 to C20 alkynyl group, or a combinationthereof, and examples of the moiety that forms a bond with the surfaceof the quantum dots may be a carboxylate (−COC⁻) moiety, a thiolate(−SH⁻) moiety, and the like.

In an embodiment, examples of the compound derived from carboxylic acidsmay include a compound derived from fatty acid such as oleate, stearate,palmitate, and the like. In an embodiment, examples of the compoundderived from the thiol may include C6 to C20 aliphatic thiolate.

For example, when the first quantum dots 141 a have hydrophobic ligandsas described above, the first light emitting layer 141 including thefirst quantum dots 141 a may also exhibit non-polarity as a whole. Inaddition, the first quantum dots to which the hydrophobic ligands areattached have solvent selectivity with respect to a non-polar solvent,specifically an aliphatic non-polar solvent. Accordingly, even if thefirst light emitting layer 141 is formed on the hole transport layer 130having solvent selectivity for the aromatic non-polar solvent by using asolution process, damage to the surface of the hole transport layer 130by an organic solvent during the formation of the first light emittinglayer 141 may be minimized.

However, an embodiment according to the invention is not limitedthereto. The second quantum dots 142 a may have the aforementionedhydrophobic ligand, and neither of the first and second quantum dots 141a and 142 a may have the aforementioned hydrophobic ligand.

For example, at least one surface of the first and second quantum dots141 a and 142 a may have a ligand having a lower solubility in anorganic solvent than quantum dots having the aforementioned hydrophobicligands attached thereto. In this case, examples of the ligand mayinclude a compound derived from a metal halide.

The metal halide may include zinc, indium, gallium, magnesium, lithium,or a combination thereof and/or may be in a form of chloride, bromide,iodide, or fluoride. The metal included in the metal halide may be thesame as the metal included in the outermost layer of the quantum dots,or may be different from each other.

Specific examples of metal halide may be zinc fluoride, zinc chloride,zinc bromide, zinc iodide, indium fluoride, indium chloride, indiumbromide, indium iodide, gallium fluoride, gallium chloride, galliumbromide, gallium iodide, magnesium fluoride, magnesium chloride,magnesium bromide, magnesium iodide, lithium fluoride, a lithiumchloride, lithium bromide, lithium iodide, or a combination thereof.

The compound derived from the metal halide may include a moiety that ischemically bound to the surface of the attached quantum dot. Examples ofthe moiety that forms a bond on the surface of the quantum dots mayinclude a halogen ion moiety (e.g., F⁻, Cl⁻, Br, I⁻). The halogen ionmoiety may be strongly bound to the surface of the quantum dots and maypassivate the quantum dots (e.g., in place of them) instead of otherligands (e.g., hydrophobic ligands such as oleic acid, etc.) present onthe surface of the quantum dots.

The compound derived from the metal halide may be obtained by reacting ametal halide solution on the light emitting layer 141 including quantumdots to which the aforementioned hydrophobic ligand is attached. Atleast a portion of the hydrophobic ligands attached to the quantum dotsmay be replaced (or substituted) with the aforementioned halogen ionmoiety. A ratio of the hydrophobic ligand attached to the surface of thequantum dots and the compound derived from the metal halide may bevariously controlled by adjusting a concentration of the metal halidesolution, a reaction time, or the like.

While not wishing to be bound by any theory, the aforementionedhydrophobic ligand may reduce luminous efficiency of quantum dotsbecause the hydrophobic moiety generally acts as a barrier againstelectron and hole injection. However, in an embodiment, the quantum dotsattached to the compound derived from the metal halide may provideimproved passivation as well as improved charge injectioncharacteristics compared with the quantum dots attached with thehydrophobic ligand.

In an embodiment, a thickness of the light emitting layer 140,specifically a sum of the thicknesses (i.e., total thickness) of thefirst and second light emitting layers 141 and 142 may be may varydepending on types and sizes of the first and second quantum dots 141 aand 142 a included in each of the first and second light emitting layers141 and 142, and types of ligands attached thereto. However, thethickness of the light emitting layer 140 may be, for example, greaterthan or equal to about 10 nm, greater than or equal to about 11 nm,greater than or equal to about 12 nm, greater than or equal to about 13nm, greater than or equal to about 14 nm, greater than or equal to about15 nm, greater than or equal to about 16 nm, greater than or equal toabout 17 nm, greater than or equal to about 18 nm, greater than or equalto about 19 nm, greater than or equal to about 20 nm, greater than orequal to about 25 nm, greater than or equal to about 30 nm, or greaterthan or equal to about 35 nm. The light emitting layer 140 may includetwo or more monolayers, for example, three or more monolayers, or fouror more monolayers of the quantum dots. The thickness of the lightemitting layer 140 may be less than or equal to about 100 nm, less thanor equal to about 90 nm, less than or equal to about 80 nm, less than orequal to about 70 nm, less than or equal to about 60 nm, less than orequal to about 50 nm, or less than or equal to about 40 nm. Thethickness of the light emitting layer 140 may be, for example, about 10nm to about 60 nm, about 15 nm to about 60 nm, about 20 nm to about 60nm, about 25 nm to about 60 nm, or about 25 nm to about 50 nm.

The electroluminescent device 10 according to an embodiment may includequantum dots in a predetermined amount to improve luminous efficiency ofthe light emitting layer 140.

For example, a total weight of the first and second quantum dots 141 aand 142 a may be included in an amount of, for example, greater than orequal to about 5 wt %, greater than or equal to about 10 wt %, greaterthan or equal to about 15 wt %, or greater than or equal to about 20 wt%, and less than or equal to about 98 wt %, less than or equal to about95 wt %, less than or equal to about 90 wt %, less than or equal toabout 85 wt %, less than or equal to about 80 wt %, less than or equalto about 75 wt %, less than or equal to about 70 wt %, less than orequal to about 65 wt %, less than or equal to about 60 wt %, less thanor equal to about 55 wt %, or less than or equal to about 50 wt %, forexample, about 5 wt % to about 98 wt %, about 20 wt % to about 98 wt %,about 20 wt % to about 90 wt %, about 20 wt % to about 85 wt %, about 50wt % to about 85 wt %, or about 50 wt % to about 80 wt % based on 100 wt% of the light emitting layer 140.

However, an embodiment according to the invention is not necessarilylimited thereto, and the total amount of the first and second quantumdots 141 a and 142 a in the light emitting layer 140 may be varieddepending on amounts of other constituent elements (e.g., a binder, anon-solvent, an organic solvent, etc.) included in the light emittinglayer 140, types and/or amounts of the used ligands, materialsconstituting the first and second quantum dots 141 a and 142 a, thenumber of shells and/or shell thickness of the core-shell structure ofthe first and second quantum dots 141 a and 142 a, wavelength ranges ofthe emitted light, thicknesses of the hole transport layer 130, thelight emitting layer 140, and/or the electron transport layer 150.

In an embodiment, the first light emitting layer 141 and the secondlight emitting layer 142 may be separate layers that are distinguishedfrom each other. For example, the first light emitting layer 141 and thesecond light emitting layer 142 may be distinguished by specificcore-shell structures of the first quantum dots 141 a and the secondquantum dots 142 a.

In an embodiment, the first light emitting layer 141 may include thefirst quantum dots 141 a described above. The first light emitting layer141 may provide holes received from the adjacent hole transport layer130 to the second light emitting layer 142, and the holes are recombinedwith electrons to emit light in a predetermined wavelength region usingthe first quantum dots 141 a.

The second light emitting layer 142 is disposed directly on the firstlight emitting layer 141 and may include the second quantum dots 142 adescribed above. The second light emitting layer 142 may provideelectrons received from the adjacent electron transport layer 150 to thefirst light emitting layer 141, and the electrons are recombined withholes to emit light in a predetermined wavelength region by using thesecond quantum dots 142 a.

In an embodiment, the first quantum dots 141 a and the second quantumdots 142 a may have core-shell structures that are distinguished fromeach other. Specifically, the first quantum dots 141 a and the secondquantum dots 142 a may be distinguished from each other in terms of thenumber of shells, and/or may be distinguished from each other in termsof shell thickness.

Hereinafter, examples of first and second quantum dots 141 a and 142 adistinguished from each other are described with reference to FIGS. 2 to5.

FIGS. 2 and 3 are cross-sectional views showing the first quantum dots(FIG. 2) and the second quantum dots (FIG. 3) of the electroluminescentdevice according to the first embodiment, respectively.

Referring to FIG. 2, the first quantum dots 141 a may include a core 141a-1 and a shell 141 a-2 surrounding the surface of the core 141 a-1. Inan embodiment, the first quantum dots 141 a may have a core-single shellstructure.

On the other hand, referring to FIG. 3, the second quantum dots 142 amay include a core 142 a-1 and multiple shells 142 a-2 including a firstshell 142 a-21 surrounding the surface of the core 142 a-1 and a secondshell 142 a-22 surrounding the first shell 142 a-21. That is, the secondquantum dots 142 a may have a core-multishell structure so as to bedistinguished from the first quantum dots 141 a. In an embodiment, thesecond quantum dots 142 a may have a core-double shell structure.

FIGS. 2 to 3 illustrate an example in which the numbers of shells of thefirst quantum dots 141 a and the second quantum dots 142 a aredifferently controlled in the electroluminescent device according to thefirst embodiment.

In a first embodiment, each of the first quantum dots 141 a and thesecond quantum dots 142 a may emit first light belonging to one of afirst wavelength region of about 380 nm to about 489 nm, a secondwavelength region of about 490 nm to about 510 nm, a third wavelengthregion of about 511 nm to about 581 nm, a fourth wavelength region ofabout 582 nm to about 610 nm, and a fifth wavelength region of about 611nm to about 680 nm. In this case, an electron transport rate may be veryhigh compared with a hole transport rate inside the electroluminescentdevice. As a result, electron/hole recombination may occur mainly on theinterface between the hole transport layer and the first light emittinglayer, and excess electrons may deteriorate the surface of the holetransport layer to decrease a life-span of a device.

While not wishing to be bound by any theory, it is likely that when thenumber of shells of the quantum dots is relatively small, the quantumdots will exhibit relatively good electron/hole transport capability.Therefore, it may be desirable to configure the first light emittinglayer 141 adjacent to the hole transport layer 130 to have a relativelygood hole transport capability and the second light emitting layer 142adjacent to the electron transport layer 150 to have a relatively lowelectron transport capability so as to suppress electron transport,respectively.

Accordingly, in the electroluminescent device 10 according to the firstembodiment, the number of shells of the first quantum dots 141 a isadjusted to be smaller than the number of shells of the second quantumdots 142 a. For example, when the first quantum dots 141 a have a singleshell, the second quantum dots 142 a may have multiple (double or more)shells. Alternatively, when the first quantum dots 141 a have double ormultiple (e.g., N−1, where N is an integer of greater than or equal to4) shells, the second quantum dots 142 a may have multiple (N, where Nis an integer of greater than or equal to 4) shells.

As a result, each of the hole transport capability per unit area and theelectron transport capability per unit area of the first quantum dotsmay be greater than or equal to the hole transport capability per unitarea and electron transport capability per unit area of the secondquantum dots. The hole transport capability per unit area and theelectron transport capability per unit area may be determined bycomparing the current density of each layer (first light emitting layerand second light emitting layer) after applying a voltage above thedriving voltage to the electroluminescent device.

Accordingly, when the number of shells of the first quantum dots 141 ais adjusted to be smaller than the number of shells of the secondquantum dots 142 a as in the electroluminescent device 10 according tothe first embodiment, the electron/hole transport capability of thefirst light emitting layer 141 may be improved while the electrontransport capability of the second light emitting layer 142 may besuppressed, and thereby it is easy to adjust the electron/holerecombination position to be between the first light emitting layer 141and the second light emitting layer 142. As such, the electroluminescentdevice 10 according to the first embodiment may exhibit improvedlife-span and/or luminescence properties and particularly improvedlife-span characteristics by adjusting the charge carrier balance.

FIGS. 4 and 5 are cross-sectional views showing the first quantum dots(FIG. 4) and the second quantum dots (FIG. 5) of the electroluminescentdevice according to the second embodiment, respectively.

Referring to FIGS. 4 to 5, the electroluminescent device according tothe second embodiment is different from the electroluminescent deviceaccording to the aforementioned first embodiment, and is an example ofthe case where the shell thicknesses of the first quantum dots 141 a′and the second quantum dots 142 a′ are differently adjusted from eachother.

Specifically, referring to FIG. 4, the first quantum dots 141 a′ mayinclude a core 141 a′-1 and a shell 141 a′-2 surrounding the surface ofthe core 141 a′-1, where the shell 141 a′-2 may be a single shell ormultiple shells (e.g., a double shell) including a first shell 141 a′-21and a second shell 141 a′-22 as illustrated in FIG. 4.

Referring to FIG. 5, the second quantum dots 142 a′ may include a core142 a′-1 and a shell 142 a′-2 surrounding the surface of the core 142a′-1, like the first quantum dots 141 a′, where the shell 142 a′-2 maybe a single shell or multiple shells (e.g., a double shell) including afirst shell 142 a′-21 and a second shell 142 a′-22 as illustrated inFIG. 5.

In the second embodiment, each of the first quantum dots 141 a and thesecond quantum dots 142 a may emit first light belonging to one of afirst wavelength region of about 380 nm to about 489 nm, a secondwavelength region of about 490 nm to about 510 nm, and a thirdwavelength region of about 511 nm to about 581 nm. In this case,although the electron transport rate is slightly faster than the holetransport rate inside the electroluminescent device, both the hole andelectron transport rates need to be improved.

While not wishing to be bound by any theory, as the shell thickness ofthe quantum dots becomes thicker, hole transport capability mayincrease, and electron transport capability may decrease. Accordingly,it may be desirable to configure the first light emitting layer 141adjacent to the hole transport layer 130 to have a relatively improvedhole transport capability, and to configure the second light emittinglayer 142 adjacent to the electron transport layer 150 to have arelatively improved electron transport capability.

Thus, in the second embodiment, a thickness (t₁) of the shell 141 a′-2constituting the first quantum dots 141 a′ may be greater than athickness (t₂) of the shell 142 a′-2 constituting the second quantumdots 142 a′.

In the second embodiment, the thickness (t₁) of the shell 141 a′-2 ofthe first quantum dots 141 a′ may be, for example, about 1 nm to about15 nm, or about 5 nm to about 15 nm.

In the second embodiment, the thickness (t₂) of the shell 142 a′-2 ofthe second quantum dots 142 a′ may be, for example, about 1 nm to about10 nm.

In the second embodiment, each of the first quantum dots 141 a′ and thesecond quantum dots 142 a′ may have a core-multishell structure, where athickness (a thickness of a single shell in the case of a single shell)of the outermost shell of the first quantum dots 141 a′ may be largerthan a thickness (a thickness of a single shell in the case of a singleshell) of the outermost shell of the second quantum dots 142 a′. Thatis, when the first and second quantum dots 141 a′ and 142 a′ havemultishells, a thickness of the outermost shell of the first quantumdots 141 a′ may be greater than a thickness of the outermost shell ofthe second quantum dots 142 a′ under conditions satisfying therelationship between the aforementioned t₁ and t₂.

As a result, the hole transport capability per unit area of the firstquantum dots 141 a′ may be greater than or equal to the hole transportcapability per unit area of the second quantum dot 142 a′, and theelectron transport capability per unit area of the first quantum dots141 a′ may be less than or equal to the electron transport capabilityper unit area of the second quantum dot 142 a′.

Therefore, as in the electroluminescent device according to the secondembodiment, when the shell thickness (t₁) of the first quantum dots 141a is adjusted to be larger than the shell thickness (t₂) of the secondquantum dots 142 a, it is easy to adjust electron/hole recombinationposition to be between the first light emitting layer 141 and the secondlight emitting layer 142, thereby improving the hole transportcapability of the first light emitting layer 141 and the electrontransport capability of the second light emitting layer 142,respectively. As such, the electroluminescent device according to thesecond embodiment may exhibit improved life-span and/or luminescenceproperties by adjusting the charge carrier balance.

In an embodiment, each of the first and second light emitting layers 141and 142 may include at least one or more monolayers, for example, atleast 1.5 or more layers of at least quantum dots.

In the case of the electroluminescent device 10 according to anembodiment, the first and second quantum dots may satisfy at least oneof a criteria (i.e., the number of shells) according to the firstembodiment and a criteria (i.e., the shell thickness) according to thesecond embodiment, and the life-span of the device. All of theaforementioned criteria may be satisfied for the purpose of improvingthe life-span and/or luminescence properties of the device.

An average thickness of each of the first and second light emittinglayers 141 and 142 may be varied depending on core-shell structures andmaterials of the first and second quantum dots 141 a and 142 a, types ofthe attached ligands, and different amounts of each light emittinglayer, but may be, for example, less than or equal to about 30 nm, lessthan or equal to about 25 nm, or less than or equal to about 20 nm andfor example, greater than or equal to about 5 nm, greater than or equalto about 5 nm 6 nm, greater than or equal to about 7 nm, greater than orequal to about 8 nm, greater than or equal to about 9 nm, greater thanor equal to about 10 nm, greater than or equal to about 11 nm, greaterthan or equal to about 12 nm, greater than or equal to about 13 nm,greater than or equal to about 14 nm, or greater than or equal to about15 nm, for example, about 5 nm to about 30 nm, about 6 nm to about 30nm, about 6 nm to about 25 nm, about 7 nm to about 25 nm, or about 8 nmto about 25 nm.

In an embodiment, the average thickness of the first light emittinglayer 141 may be equal to or greater than the average thickness of thesecond light emitting layer 142. For example, the average thickness ofthe first light emitting layer 141 may be greater than the averagethickness of the second light emitting layer 142.

In an embodiment, the average thickness of the light emitting layers140, that is, a total average thickness of each average thickness of thefirst and second light emitting layers 141 and 142 (i.e., an average ofthe sum of the thicknesses of the first and second light emitting layers141 and 142) may be, for example, less than or equal to about 60 nm,less than or equal to about 55 nm, less than or equal to about 50 nm,less than or equal to about 45 nm, or less than or equal to about 40 nmand for example, greater than or equal to about 10 nm, greater than orequal to about 15 nm, greater than or equal to about 20 nm, greater thanor equal to about 25 nm, or greater than or equal to about 30 nm, andfor example, about 10 nm to about 60 nm, about 10 nm to about 55 nm,about 10 nm to about 50 nm, about 15 nm to about 50 nm, about 15 nm toabout 5 nm, or about 15 nm to about 40 nm.

In an embodiment, the electron transport layer 150 may be disposedbetween the light emitting layer 140 and the second electrode 160 and,for example, directly on the second light emitting layer 142 totransport electrons to the light emitting layer 140.

In an embodiment, a thickness of the electron transport layer 150 may beadjusted in consideration of an electron-hole balance with the holeinjection layer 120, the hole transport layer 130, and/or the lightemitting layer 140 in the device, but may be, for example, greater thanor equal to about 10 nm, greater than or equal to about 15 nm, orgreater than or equal to about 20 nm, and for example, less than orequal to about 100 nm, less than or equal to about 90 nm, less than orequal to about 80 nm, less than or equal to about 70 nm, less than orequal to about 60 nm, less than or equal to about 50 nm, or less than orequal to about 40 nm, or for example, about 10 nm to about 100 nm, about10 nm to about 60 nm, about 10 nm to about 50 nm, about 10 mm to about40 nm, or about 15 nm to about 40 nm.

When the electron transport layer 150 has a thickness out of the aboverange, the void, the crack, and the like on the electron transport layer150 have a more influence on electron transport properties and thusgreatly deteriorate device characteristics and hardly accomplish anelectron-hole balance with the other constituent elements in theelectroluminescent device 10.

In an embodiment, the electron transport layer 150 may be formed of orinclude an electron-transporting material not emitting light by anelectric field and thus not internally quenching electrons.

The electron transport layer 150 may include inorganic materialnanoparticles or may be an organic layer formed by deposition. Forexample, the electron transport layer 150 may include inorganic materialnanoparticles, a quinolone-based compound, a triazine-based compound, aquinoline-based compound, a triazole-based compound, a naphthalene-basedcompound, or a combination thereof.

In an embodiment, the electron transport layer 150 may include inorganicmaterial nanoparticles. The inorganic material nanoparticles may impartelectron transport properties to the electron transport layer 150 and donot exhibit light emitting properties. Examples of the inorganicmaterial nanoparticles may be salts of metals including zinc (Zn),magnesium (Mg), tin (Sn), zirconium (Zr), titanium (Ti), aluminum (Al),or a combination thereof.

In an embodiment, the electron transport layer 150 may include two ormore inorganic material nanoparticles. In an embodiment, the electrontransport layer 150 may include a cluster layer consisting of aplurality of inorganic material nanoparticles. In an embodiment, theelectron transport layer 150 may be a cluster layer consisting of two ormore inorganic material nanoparticles.

An electron injection layer to facilitate the injection of electronsand/or a hole blocking layer to prevent the movement of holes may befurther disposed between the electron transport layer 150 and the secondelectrode 160. Thicknesses of the electron injection layer and the holeblocking layer may be selected appropriately. For example, eachthickness of the layers may be greater than or equal to about 1 nm orless than or equal to about 500 nm, but the invention is not limitedthereto. The electron injection layer may be an organic layer formed bydeposition.

The electron injection layer and/or the hole blocking layer may include,for example, at least one selected from1,4,5,8-naphthalene-tetracarboxylic dianhydride (“NTCDA”), bathocuproine(“BCP”), tris[3-(3-pyridyl)-mesityl]borane (“3TPYMB”), LiF, Alq₃, Gaq₃,Inq₃, Znq₂, Zn(“BTZ”)₂, BeBq₂, Liq, n-type metal oxide (e.g., ZnO, HfO₂,etc.), Bphen, and a combination thereof, but the invention is notlimited thereto.

As described above, the electroluminescent device 10 according to anembodiment is configured to have the distinguished core-shell structuresof the first and second quantum dots 141 a and 142 a from each othersuch that the charge carrier balance inside the device may be easilyadjusted, for example, electron/hole recombination position may beadjusted to be between the first light emitting layer 141 and the secondlight emitting layer 142. As a result, the electroluminescent device 10according to an embodiment may exhibit improved life-span and/orluminescence properties.

Hereinafter, a display device including the aforementionedelectroluminescent device 10 is described.

A display device according to an embodiment includes a substrate, adriving circuit disposed on the substrate, and a firstelectroluminescent device, a second electroluminescent device, and athird electroluminescent device spaced apart from each other in apredetermined interval and disposed on the driving circuit.

The first to third electroluminescent devices have the same structure asthe electroluminescent device 10, but the wavelengths of the lightsemitted from each quantum dots may be different from each other.

In an embodiment, the first electroluminescent device may be a reddevice emitting red light, the second electroluminescent device may be agreen device emitting green light, and the third electroluminescentdevice may be a blue device emitting blue light. In other words, thefirst to third electroluminescent devices may be pixels expressing red,green, and blue, respectively, in the display device.

However, an embodiment according to the invention is not necessarilylimited thereto, but the first to third electroluminescent devices mayexpress magenta, yellow, cyan, or may express other colors,respectively.

One of the first to third electroluminescent devices may be theelectroluminescent device 10. For example, the first electroluminescentdevice displaying red and/or the third electroluminescent devicedisplaying blue may be desirably the aforementioned electroluminescentdevice 10.

In the display device according to an embodiment, a hole injectionlayer, a hole transport layer, an electron transport layer, an electroninjection layer, and a hole blocking layer except a light emitting layerof each pixel may be integrated to form a common layer. However, anembodiment according to the invention is not limited thereto. A holeinjection layer, a hole transport layer, an electron transport layer, anelectron injection layer, and a hole blocking layer may be independentlydisposed in each pixel of the display device, or at least one of a holeinjection layer, a hole transport layer, an electron transport layer, anelectron injection layer, and a hole blocking layer may form a commonlayer and remaining layers may form a separate independent layer.

The substrate may be a transparent insulating substrate or may be madeof a ductile material. The substrate may include glass or a polymermaterial in a film having a glass transition temperature (Tg) of greaterthan about 150° C. For example, it includes a COC (cycloolefincopolymer) or COP (cycloolefin polymer) based material. All the first tothird electroluminescent devices are disposed on the substrate. That is,a substrate of the display device according to an embodiment provides acommon layer.

The driving circuit is disposed on the substrate and is independentlyconnected to each of the first to third electroluminescent devices. Thedriving circuit may include at least one line including a scan line, adata line, a driving power source line, a common power source line, andthe like, at least two of thin film transistors (“TFT”) connected to thewire and corresponding to one organic light emitting diode, and at leastone capacitor, or the like. The driving circuit may have a variety ofthe known structures.

As described above, a display device according to an embodiment mayexhibit improved device efficiency and thus improved life-span andluminous efficiency.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. These examples, however, are not in any sense tobe interpreted as limiting the scope of the invention.

Verification Example 1

A glass substrate deposited with ITO as a first electrode (an anode) issurface-treated with UV-ozone for 15 minutes, and a PEDOT: PSS solution(HOMO energy level: −5.35 eV, HC Starks) is spin-coated thereon andheat-treated 150° C. for 30 minutes under a nitrogen atmosphere to forma 30 nm-thick hole injection layer. Here, HOMO stands for highestoccupied molecular orbital.

On the hole injection layer (TFB, an HOMO energy level: −5.56 eV, a LUMOenergy level: −2.69 eV, Sumitomo Co., Ltd.), a solution prepared bydissolving poly[(9,9-dioctylfluorenyl-2,7-diyl-co(4,4′-(N-4-butylphenyl)diphenylamine] in o-xylene is spin-coated and heat-treated at 150° C.for 30 minutes to form a 25 nm-thick first hole transport layer. Here,LUMO stands for lowest unoccupied molecular orbital.

Subsequently, a composition for a light emitting layer, which isprepared by dispersing an InP/ZnSe core-single shell quantum dot towhich oleate as a hydrophobic ligand is attached (an average particlediameter: 18 nm, a peak emission wavelength: 630 nm) in octane is coatedand heated at 80° C. to form a 20 nm-thick (red) light emitting layer.

On the light emitting layer, a bicarbazole-based compound (GSH0137,Samsung SDI Co.) is deposited to form a 36 nm-thick second holetransport layer.

Subsequently, on the second hole transport layer,1,4,5,8,9,11-Hexaazatriphenylenehexacar-bonitrile (HAT-CN) is depositedto form a 10 nm-thick hole injection layer (“HIL”).

On the hole injection layer (HIL), aluminum is vacuum-deposited to forma 100 nm-thick second electrode and thus produce HOD (Hole Only Device)according to Verification Example 1 (ITO/PEDOT:PSS/TFB/RedQD(InP/ZnSe)/GSH0137/HAT-CN/Ag).

Verification Example 2

HOD (Hole Only Device) according to Verification Example 2(ITO/PEDOT:PSS/TFB/Red QD (InP/ZnSe/ZnS)/GSH0137/HAT-CN/Ag) is producedaccording to the same method as Verification Example 1 except that anInP/ZnSe/ZnS core-double shell quantum dot to which oleate as ahydrophobic ligand is attached (an average particle diameter: 18 nm, apeak emission wavelength: 630 nm) is used instead of the InP/ZnSecore-single shell quantum dot to which oleate as a hydrophobic ligand isattached.

Verification Example 3

An ITO-deposited glass substrate as a first electrode (an anode) issurface-treated with UV-ozone for 15 minutes, and a solution for anelectron transport layer, which is prepared by dispersing ZnMgO (anaverage particle diameter: 2 nm to 5 nm) in ethanol, is spin-coatedthereon and heat-treated at 80° C. for 30 minutes to form a 20 nm-thickfirst electron transport layer.

Subsequently, a composition for a light emitting layer, which isprepared by dispersing an InP/ZnSe core-single shell quantum dot towhich oleate as a hydrophobic ligand is attached (an average particlediameter: 18 nm, a peak emission wavelength: 630 nm) in octane, isspin-coated and heat-treated at 80° C. to form a 20 nm-thick (red) lightemitting layer.

On the light emitting layer, a solution for an electron transport layer,which is prepared by dispersing ZnMgO (average particle diameter: 2 nmto 5 nm) in ethanol, is spin-coated and heat-treated at 80° C. for 30minutes to form a 20 nm-thick second electron transport layer.

Subsequently, on the second electron transport layer, aluminum isvacuum-deposited to form a 100 nm-thick second electrode and thusproduce EOD (Electron Only Device) according to Verification Example 3(ITO/ZnMgO/Red QD (InP/ZnSe)/ZnMgO/Al).

Verification Example 4

EOD (Electron Only Device) according to Verification Example 4(ITO/ZnMgO/Red QD (InP/ZnSe/ZnS)/ZnMgO/Al) is produced according to thesame method as Verification Example 3 except that an InP/ZnSe/ZnScore-double shell quantum dot to which oleate as a hydrophobic ligand isattached (an average particle diameter: 18 nm, a peak emissionwavelength: 630 nm) is used instead of the InP/ZnSe core-single shellquantum dot to which oleate as a hydrophobic ligand is attached.

Evaluation 1: Charge Transport Capability of Red Light Emitting Device

Voltage-current density of HOD's according to Verification Examples 1 to2 and EOD's according to Verification Examples 3 to 4 are respectivelymeasured, and the results are shown in FIGS. 6 to 7.

FIG. 6 shows voltage-current density graphs of HOD's (Hole Only Device)according to Verification Examples 1 to 2, and FIG. 7 showsvoltage-current density graphs of HOD's (Hole Only Device) according toVerification Examples 3 to 4.

Referring to FIG. 6, Verification Example 1 including the InP/ZnSecore-single shell quantum dot exhibits excellent current densitycompared with Verification Example 2 including the InP/ZnSe/ZnSeScore-double shell quantum dot.

On the other hand, referring to FIG. 7, Verification Example 3 includingthe InP/ZnSe core-single shell quantum dot exhibits excellent currentdensity compared with Verification Example 4 including theInP/ZnSe/ZnSeS core-double shell quantum dot.

Considering that current density indicates charge (electron and hole)transport capability per unit area, a red light emitting layer includingthe InP/ZnSe core-single shell quantum dot has excellent charge(electron and hole) transport capability compared with a red lightemitting layer including the InP/ZnSe/ZnSeS core-double shell quantumdot.

Accordingly, in a red light emitting device, the red light emittinglayer including the InP/ZnSe core-single shell quantum dot has excellenthole transport capability and thus may be applied as a first lightemitting layer neighboring the hole transport layer, and the red lightemitting layer including the InP/ZnSe/ZnSeS core-double shell quantumdot has a little low electron transport capability and thus may beapplied as a second light emitting layer neighboring the electrontransport layer.

Verification Example 5

HOD (Hole Only Device) according to Verification Example 5(ITO/PEDOT:PSS/TFB/Blue QD (ZnTeSe/ZnSe/ZnS, shell thickness:9nm)/GSH0137/HAT-CN/Ag) is produced according to Verification Example 1except that a ZnTeSe/ZnSe/ZnS core-double shell quantum dot to whicholeate as a hydrophobic ligand is attached (an average particlediameter: 10 nm to 12 nm, a shell thickness: 9 nm, a peak emissionwavelength: 455 nm) is used instead of the InP/ZnSe core-single shellquantum dot to which oleate as a hydrophobic ligand is attached.

Verification Example 6

HOD (Hole Only Device) according to Verification Example 6(ITO/PEDOT:PSS/TFB/Blue QD (ZnTeSe/ZnSe/ZnS, shell thickness: 5nm)/GSH0137/HAT-CN/Ag) is produced according to Verification Example 1except that a ZnTeSe/ZnSe/ZnS core-double shell quantum dot to whicholeate as a hydrophobic ligand is attached (an average particlediameter: 10 nm to 12 nm, a shell thickness: 5 nm, a peak emissionwavelength: 455 nm) is used instead of the InP/ZnSe core-single shellquantum dot to which oleate as a hydrophobic ligand is attached.

Verification Example 7

EOD (Electron Only Device) according to Verification Example 7(ITO/ZnMgO/Blue QD (ZnTeSe/ZnSe/ZnS, a shell thickness: 9 nm)/ZnMgO/Al)is produced according to Verification Example 3 except that aZnTeSe/ZnSe/ZnS core-double shell quantum dot (an average particlediameter: 10 nm to 12 nm, a shell thickness: 9 nm, a peak emissionwavelength: 455 nm) is used instead of the InP/ZnSe core-single shellquantum dot to which oleate as a hydrophobic ligand is attached.

Verification Example 8

EOD (Electron Only Device) according to Verification Example 8(ITO/ZnMgO/Blue QD (ZnTeSe/ZnSe/ZnS, shell thickness: 5 nm)/ZnMgO/Al) isproduced according to Verification Example 3 except that aZnTeSe/ZnSe/ZnS core-double shell quantum dot to which oleate as ahydrophobic ligand is attached (an average particle diameter: 10 nm to12 nm, a shell thickness: 5 nm, a peak emission wavelength: 455 nm) isused instead of the InP/ZnSe core-single shell quantum dot to whicholeate as a hydrophobic ligand is attached.

Evaluation 2: Charge Transport Capability of Blue Light Emitting Device

Voltage-current density of HOD's according to Verification Examples 5 to6 and EOD's according to Verification Examples 7 to 8 are respectivelymeasured, and the results are shown in FIGS. 8 to 9.

FIG. 8 shows voltage-current density graphs of HOD's (Hole Only Device)according to Verification Examples 5 to 6, and FIG. 9 showsvoltage-current density graphs of HOD's (Hole Only Device) according toVerification Examples 7 to 8.

Referring to FIG. 8, Verification Example 5 including a ZnTeSe/ZnSe/ZnSquantum dot having a relatively thick shell exhibits excellent currentdensity compared with Verification Example 6 including a ZnTeSe/ZnSe/ZnSquantum dot having a relatively thin shell.

On the other hand, referring to FIG. 9, Verification Example 8 includinga ZnTeSe/ZnSe/ZnS quantum dot having a relatively thick shell exhibitsexcellent current density compared with Verification Example 7 includinga ZnTeSe/ZnSe/ZnS quantum dot having a relatively thick shell.

Considering that current density indicates charge (electron and hole)transport capability per unit area, a blue light emitting layerincluding a ZnTeSe/ZnSe/ZnS quantum dot having a relatively thick shellexhibits relatively excellent hole transport capability, and a bluelight emitting layer including a ZnTeSe/ZnSe/ZnS quantum dot having arelatively thin shell exhibits relatively excellent electron transportcapability.

Accordingly, in a blue light emitting device, the blue light emittinglayer including the ZnTeSe/ZnSe/ZnS quantum dot having a relativelythick shell exhibits excellent hole transport capability and thus may beapplied as a first light emitting layer neighboring the hole transportlayer, and the blue light emitting layer including the ZnTeSe/ZnSe/ZnSquantum dot having a relatively thin shell exhibits excellent electrontransport capability and thus may be applied as a second light emittinglayer neighboring the electron transport layer.

Example 1

A glass substrate deposited with ITO (a work function: −4.850 eV) as afirst electrode (an anode) is surface-treated with UV-ozone for 15minutes, and a PEDOT:PSS solution (an HOMO energy level: −5.35 eV, aLUMO energy level: −2.75 eV, H.C. Starks) is spin-coated andheat-treated 150° C. for 30 minutes under a nitrogen atmosphere to forma hole injection layer having a thickness of 30 nm to 40 nm.

Then, a solution in whichpoly[(9,9-dioctylfluorenyl-2,7-diyl-co(4,4′-(N-4-butylphenyl)diphenylamine] on the hole injection layer (TFB, HOMO energy level:−5.56 eV, LUMO energy level: −2.69 eV, Sumitomo Co., Ltd.) dissolved intoluene on the hole injection layer and heat-treated at 150° C. for 30minutes to form a 25 nm-thick first hole transport layer.

On the hole injection layer (HIL),poly[(9,9-dioctylfluorenyl-2,7-diyl-co(4,4′-(N-4-butylphenyl)diphenylamine] (TFB, a HOMO energy level: −5.56eV, a LUMO energy level: −2.69 eV, Sumitomo Co. Ltd.) is dissolved intoluene, and the solution is spin-coated on the hole injection layer andheat-treated at 150° C. for 30 minutes to form a 25 nm-thick holetransport layer.

Subsequently, a composition for a first red light emitting layer isprepared by adding 150 mg of an InP/ZnSe core-single shell red quantumdot to which oleate as a hydrophobic ligand is attached on the surface(an average particle diameter: 18 nm, a peak wavelength: 630 nm) to 10mL of octane and stirred the mixture for 5 minutes. Subsequently, thecomposition for a first red light emitting layer is spin-coated on thehole transport layer and then, surface-washed with ethanol andheat-treated at 80° C. for 30 minutes under a nitrogen atmosphere toform a 20 nm-thick first red light emitting layer.

On the other hand, 15 mg/mL of an InP/ZnSe/ZnS core-double shell redquantum dot to which oleate as a hydrophobic ligand is attached (anaverage particle diameter: 11 nm to 13 nm, a peak wavelength: about 453nm) is added to 10 mL of octane and then, stirred for 5 minutes toprepare a composition for a second red light emitting layer.

Subsequently, the composition for a second red light emitting layer isspin-coated on the first red light emitting layer and then, heat-treatedat 80° C. for 30 minutes under a nitrogen atmosphere to form a 10nm-thick second red light emitting layer.

On the second red light emitting layer, a solution for an electrontransport layer, which is prepared by dispersing ZnMgO (an averageparticle diameter: 3 nm, an HOMO energy level: −7.6 eV, a LUMO energylevel: −4.3 eV) in ethanol, spin-coated and heat-treated at 80° C. for30 minutes to form a 20 nm to 25 nm-thick electron transport layer.

On the electron transport layer, aluminum (a work function: −4.3 eV) isvacuum-deposited to form a 100 nm-thick second electrode and thusproduce an electroluminescent device according to Example 1[ITO/PEDOT:PSS/TFB/Red QD (InP/ZnSe)/Red QD (InP/ZnSe/ZnS)/ZnMgO/Al].

Comparative Example 1

An electroluminescent device according to Comparative Example 1 isproduced according to the same method as Example 1 except that acomposition for a first red light emitting layer instead of thecomposition for a second red light emitting layer is once more coated onthe first red light emitting layer to form a second red light emittinglayer.

[ITO/PEDOT:PSS/TFB/Red QD (InP/ZnSe)/Red QD (InP/ZnSe)/ZnMgO/Al].

Evaluation 3: Luminescence and Life-Span Properties of Red LightEmitting Device

Luminescence properties of the red electroluminescent devices accordingto Example 1 and Comparative Example 1 are evaluated, and the resultsare shown in Table 1 and FIG. 10.

TABLE 1 Peak Full width Maximum Driving emission at half Maximum MaximumEQE @ EQE@ EQE@ luminous voltage Luminance wave- maximum EQE luminance5000 nt 10000 nt 50000 nt intensity @5 mA @5 mA length (FWHM) [%][cd/m²] [%] [%] [%] [cd/A] [V] [Cd/m²] [nm] [nm] Ex. 1 9.9 104550 9.89.2 6.8 11.2 2.7 536 630 34 Comp. 13.6 96020 13.0 11.7 6.7 15.8 2.9 773630 35 Ex. 1

Here, cd/m² is Candela per Square Meter, cd/A is Candela per Ampere, andV is voltages. FIG. 10 shows voltage-current density graphs of theelectroluminescent devices according to Example 1 and ComparativeExample 1. Referring to Table 1 and FIG. 10, the electroluminescentdevice of Example 1 exhibits equivalent luminescence properties withthat of Comparative Example 1 and particularly, a little low drivingvoltage compared with that of Comparative Example 1.

Accordingly, referring to the results of Table 1 and FIG. 10,luminescence properties and particularly, a driving voltage of theelectroluminescent device may be reduced by adjusting the number of theshells of the core-shell quantum dots included in the dual lightemitting layer.

On the other hand, life-span characteristics of the electroluminescentdevices according to Example 1 and Comparative Example 1 are evaluated,and the results are shown in Table 2 and FIGS. 11 to 12.

TABLE 2 Initial Initial T95 T50 Current P. current voltage [h] [h] [mA][μA] [V] Ex. 1 8.34 248.9 0.409 6.061 3.2 Comp. Ex. 1 1.39 165.7 0.2895.815 3.3

In Table 2, T95 and T50 respectively indicate time when 95% (T95) and50% (T50) of luminance appear relative to initial luminance. On theother hand, in Table 2, Initial P. current is a current value convertedfrom emitted light through a light-receiving sensor (a photodiode)during operation of a device and indicates emitted light intensity ofthe device. Here, mA is milli-amperes, and μA is micro-amperes. In otherwords, the Initial P. current means that the electroluminescent devicesof Examples and Comparative Examples are measured with substantiallyequivalent light intensity.

FIG. 11 shows time-luminance graphs of the electroluminescent devicesaccording to Example 1 and Comparative Example 1, and FIG. 12 showstime-voltage graphs of the electroluminescent devices according toExample 1 and Comparative Example 1.

Referring to Table 2 and FIGS. 11 to 12, the electroluminescent deviceof Example 1 exhibits relatively reduced device degradation depending ontime changes as well as greatly improved T95 and T50 compared withComparative Example 1 (refer to FIG. 12).

Accordingly, referring to the results of Table 2 and FIGS. 11 to 12,life-span characteristics of the electroluminescent devices may begreatly improved by differently adjusting the number of the shells ofthe core-shell quantum dots in the dual light emitting layer.

Example 2

A glass substrate deposited with ITO (a work function: −4.850 eV) as afirst electrode (an anode) is surface-treated with UV-ozone for 15minutes, and a PEDOT:PSS solution (an HOMO energy level: −5.35 eV, aLUMO energy level: −2.75 eV, H.C. Starks) is spin-coated andheat-treated at 150° C. for 30 minutes under a nitrogen atmosphere toform a hole injection layer having a thickness of 30 nm to 40 nm.

On the hole injection layer, a solution prepared by dissolvingpoly[(9,9-dioctylfluorenyl-2,7-diyl-co(4,4′-(N-4-butylphenyl)diphenylamine](TFB, an HOMO energy level: −5.56 eV, a LUMO energy level: −2.69 eV,Sumitomo Co., Ltd.) in toluene is spin-coated on the hole injectionlayer and heat-treated at 150° C. for 30 minutes to form a 25 nm-thickhole transport layer.

Subsequently, a composition for a first blue light emitting layer isprepared by adding 150 mg of a ZnTeSe/ZnSe/ZnS core-double shell bluequantum dot to which oleate as a hydrophobic ligand is attached on thesurface (an average particle diameter: 10 nm to 12 nm, a shell averagethickness: 9 nm, a peak wavelength: 455 nm) to 10 mL of octane andstirring the mixture for 5 minutes. The composition for a first bluelight emitting layer is spin-coated on the hole transport layer andheat-treated at 80° C. for 30 minutes under a nitrogen atmosphere toform a 28 nm-thick first blue light emitting layer.

Then, an ethanol solution of zinc chloride (a concentration: 10 mg/mL)is added in a dropwise fashion on the first blue light emitting layerand reacted for one minute to substitute chloride for the oleate adheredto the quantum dot of the first blue light emitting layer. Subsequently,the first blue light emitting layer is dried at 120° C. for 30 minutesunder a vacuum condition.

On the other hand, 15 mg/mL of a ZnTeSe/ZnSe/ZnS core-double shell bluequantum dot to which oleate as a hydrophobic ligand is attached on thesurface (an average particle diameter: 10 nm to 12 nm, an average shellthickness: 5 nm, a peak wavelength: 455 nm) is added to 10 mL of octaneand stirred the mixture for 5 minutes to prepare a composition for asecond blue light emitting layer.

Subsequently, the composition for a second blue light emitting layer isspin-coated on the first blue light emitting layer and heat-treated at80° C. for 30 minutes under a nitrogen atmosphere to form a 13 nm-thicksecond blue light emitting layer.

On the second blue light emitting layer, a solution for an electrontransport layer, which is prepared by dispersing ZnMgO (an averageparticle diameter: 3 nm, an HOMO energy level: −7.6 eV, a LUMO energylevel: −4.3 eV) in ethanol is spin-coated and heat-treated at 80° C. for30 minutes to form a 20 nm to 25 nm-thick electron transport layer.

Subsequently, on the electron transport layer, aluminum (a workfunction: −4.3 eV) is vacuum-deposited to form a 100 nm-thick secondelectrode and thus produce an electroluminescent device according toExample 2 [ITO/PEDOT:PSS/TFB/Blue QD (ZnTeSe/ZnSe/ZnS, a shellthickness: 9 nm)/Blue QD (ZnTeSe/ZnSe/ZnS, a shell thickness: 5nm)/ZnMgO/Al].

Comparative Example 2

An electroluminescent device according to Comparative Example 2 isproduced according to the same method as Example 2 except that the firstthe composition for a blue light emitting layer instead of thecomposition for a second blue light emitting layer is once morespin-coated on the first blue light emitting layer to form a second bluelight emitting layer. [ITO/PEDOT:PSS/TFB/Blue QD (ZnTeSe/ZnSe/ZnS, shellthickness: 9 nm)/Blue QD (ZnTeSe/ZnSe/ZnS, shell thickness: 9nm)/ZnMgO/Al].

Evaluation 4: Luminescence and Life-Span Properties of Blue LightEmitting Device

Luminescence properties of the blue electroluminescent devices accordingto Example 2 and Comparative Example 2 are evaluated, and the resultsare shown in Table 3 and FIGS. 13 to 14.

TABLE 3 Peak Full width Maximum Driving emission at half Maximum MaximumEQE@ EQE@ EQE@ luminous voltage @ Luminance Voltage@ wave- maximum EQEluminance 1000 nt 5000 nt 10000 nt intensity 5 mA @5 mA 325 nit length(FWHM) [%] [cd/m²] [%] [%] [%] [cd/A] [V] [Cd/m²] [V] [nm] [nm] Ex. 29.4 31010 9.2 7.7 6.8 7.1 3.1 352 3.0 455 24 Comp. 8.0 24210 7.7 6.6 5.75.9 3.1 286 3.1 455 24 Ex. 2

FIG. 13 shows voltage-luminance graphs of the electroluminescent devicesaccording to Example 2 and Comparative Example 2, and FIG. 14 showsluminance-external quantum efficiency (EQE) graphs of theelectroluminescent devices according to Example 2 and ComparativeExample 2.

Referring to Table 3 and FIGS. 13 to 14, the electroluminescent deviceof Example 2 exhibits excellent luminescence properties andspecifically, external quantum efficiency, luminance, maximum luminousintensity, and the like compared with those of Comparative Example 2.

Accordingly, referring to the results of Table 3 and FIGS. 13 to 14,luminescence properties of the electroluminescent devices may be greatlyimproved, even though the core-shell quantum dots included in the duallight emitting layer are adjusted to have a different shell thickness.

On the other hand, life-span characteristics of the electroluminescentdevices according to Example 2 and Comparative Example 2 are evaluated,and the results are shown in Table 4 and FIGS. 15 to 16.

TABLE 4 Initial P. Initial Voltage Initial voltage − T95 T50 Currentcurrent voltage @T50 voltage@T50 [h] [h] [mA] [μA] [V] [V] [V] Ex. 23.93 42.4 0.232 3.080 3.0 3.8 0.8 Comp. 2.57 17.7 0.270 3.055 3.1 4.31.2 Ex. 2

In Table 4, T95, T50, and Initial P. current are equally defined as usedin Table 2. FIG. 15 shows time-luminance graphs of theelectroluminescent devices according to Example 2 and ComparativeExample 2, and FIG. 16 shows time-voltage graphs of theelectroluminescent devices according to Example 2 and ComparativeExample 2.

Referring to Table 4 and FIGS. 15 to 16, the electroluminescent deviceof Example 2 exhibits greatly improved T95 and T50 and in addition,relatively small device degradation depending on a time change (refer toFIG. 16) compared with those of Comparative Example 2.

Accordingly, referring to the results of Table 4 and FIGS. 15 to 16,even though the core-shell quantum dots included in the dual lightemitting layer are adjusted to have a shell thickness, life-spancharacteristics of the electroluminescent device are greatly improved.

While this disclosure has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

DESCRIPTION OF SYMBOLS

10: electroluminescent device 100: substrate 110: first electrode 120:hole injection layer 130: hole transport layer 140: light emitting layer141: first light emitting layer 141a: first quantum dot 142: secondlight emitting layer 142a: second quantum dot 150: electron transportlayer 160: second electrode

What is claimed is:
 1. An electroluminescent device, comprising a firstelectrode and a second electrode which face each other; a hole transportlayer disposed between the first electrode and the second electrode; alight emitting layer comprising: a first light emitting layer disposedbetween the hole transport layer and the second electrode, the firstlight emitting layer comprising a first quantum dot, and a second lightemitting layer disposed between the first light emitting layer and thesecond electrode, the second light emitting layer comprising a secondquantum dot; and an electron transport layer disposed between the lightemitting layer and the second electrode, wherein each of the first lightemitting layer and the second light emitting layer emits first light,each of the first quantum dot and the second quantum dot has acore-shell structure, the core-shell structure includes one or moreshells, and the first quantum dot and the second quantum dot havedifferent numbers of shells from each other or have different totalthicknesses of the one or more shells from each other.
 2. Theelectroluminescent device of claim 1, wherein the core comprises a firstsemiconductor nanocrystal, and the shell comprises a secondsemiconductor nanocrystal having a composition different from acomposition of the first semiconductor nanocrystal.
 3. Theelectroluminescent device of claim 2, wherein the first semiconductornanocrystal and the second semiconductor nanocrystal independentlycomprise a Group II-VI compound that does not comprise Cd, a Group III-Vcompound, a Group IV-VI compound, a Group IV element or compound, aGroup compound, a Group I-II-IV-VI compound that does not comprise Cd,or a combination thereof.
 4. The electroluminescent device of claim 1,wherein the number of shells of the first quantum dot is less than thenumber of shells of the second quantum dot.
 5. The electroluminescentdevice of claim 4, wherein the first quantum dot has a core-single shellstructure and the second quantum dot comprises a core-multiple shellstructure.
 6. The electroluminescent device of claim 4, wherein holetransport capability per unit area of the first quantum dot is greaterthan hole transport capability per unit area of the second quantum dot,and electron transport capability per unit area of the first quantum dotis greater than electron transport capability per unit area of thesecond quantum dot.
 7. The electroluminescent device of claim 1, whereinthe total thickness of the one or more shells in the first quantum dotis greater than the total thickness of the one or more shells in thesecond quantum dot.
 8. The electroluminescent device of claim 7, whereinthe total thickness of the one or more shells in the first quantum dotis about 1 nanometers (nm) to about 15 nm, and the total thickness ofthe one or more shells in the second quantum dot is about 1 nm to about10 nm.
 9. The electroluminescent device of claim 7, wherein each of thefirst quantum dot and the second quantum dot has a core-multishellstructure, and a thickness of an outermost shell of the multishells ofthe first quantum dot is greater than a thickness of an outermost shellof the multishells of the second quantum dot.
 10. The electroluminescentdevice of claim 7, wherein the first quantum dot has lower electrontransport capability than the second quantum dot.
 11. Theelectroluminescent device of claim 7, wherein hole transport capabilityper unit area of the first quantum dot is greater than or equal to holetransport capability per unit area of the second quantum dot, andelectron transport capability per unit area of the first quantum dot isless than or equal to electron transport capability per unit area of thesecond quantum dot.
 12. The electroluminescent device of claim 1,wherein the first light belongs to any one of a first wavelength regionof about 380 nm to about 489 nm, a second wavelength region of about 490nm to about 510 nm, a third wavelength region of about 511 nm to about581 nm, a fourth wavelength region of about 582 nm to about 610 nm, anda fifth wavelength region of about 611 nm to about 680 nm.
 13. Theelectroluminescent device of claim 1, wherein a ligand comprising acompound derived from a metal halide, a compound derived from acarboxylic acid, a compound derived from a thiol, or a combinationthereof is attached to a surface of each of the first quantum dot andthe second quantum dot.
 14. The electroluminescent device of claim 1,wherein each of the first light emitting layer and the second lightemitting layer has an average thickness of about 5 nm to about 30 nm.15. The electroluminescent device of claim 1, wherein an averagethickness of the first light emitting layer is greater than or equal toan average thickness of the second light emitting layer.
 16. Theelectroluminescent device of claim 1, wherein the hole transport layercomprises a poly(3,4-ethylenedioxythiophene) derivative, a poly(styrenesulfonate) derivative, a poly-N-vinylcarbazole derivative, apolyphenylenevinylene derivative, a polyparaphenylenevinylenederivative, a polymethacrylate derivative, a polyarylamine derivative, apolyaniline derivative, a polypyrrole derivative, apoly(9,9-dioctylfluorene) derivative, a poly(spiro-bifluorene)derivative, tris(4-carbazol-9-yl phenyl)amine (TCTA),N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(TPD), N,N′-di(naphthalen-1-yl)-N-N′-diphenyl-benzidine (NPB),tris(3-methylphenylphenylamino)-triphenylamine (m-MTDATA),dipyrazino[2,3-f:2′, 3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile(HAT-CN), poly-TPD, NiO, MoO₃, or a combination thereof.
 17. Theelectroluminescent device of claim 1, wherein the electron transportlayer comprises inorganic material nanoparticles, quinolone-basedcompounds, triazine-based compounds, quinoline-based compounds,triazole-based compounds, naphthalene-based compounds, or a combinationthereof.
 18. The electroluminescent device of claim 17, wherein theelectron transport layer comprises a cluster layer composed of inorganicmaterial nanoparticles.
 19. The electroluminescent device of claim 1,wherein a hole injection layer is further included between the firstelectrode and the hole transport layer.
 20. A display device comprisingthe electroluminescent device of claim 1.